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Igaragaza akazu k'amaslayidi atatu icyarimwe. Koresha utubuto twa Mbere n'Utukurikira kugira ngo unyure muri slayidi eshatu icyarimwe, cyangwa ukoreshe utubuto twa slayidi ku iherezo kugira ngo unyure muri slayidi eshatu icyarimwe.
Ibyuma bitagira umugese bikoreshwa cyane hamwe n’uburyo bwabyo bukozwemo birwanya ingese mu bihe biri hagati bitewe n’urwego rw’ingufu rugizwe na chromium oxyde. Ingufu n’isenyuka ry’icyuma bikunze kujyana no kwangirika kw’ibi bice, ariko gake cyane bitewe no kugaragara k’ubusumbane bw’ubuso, bitewe n’urwego rwa mikorosikopi. Muri iki gikorwa, heterogeneity y’ubuso bw’ibinyabutabire bya nanoscale, byagaragaye hakoreshejwe mikorosikopi ya spectroscopic na chemometric analysis, byiganje mu buryo butunguranye ivunika n’isenyuka ry’icyuma gikozwe muri cerium modified super duplex stainless steel 2507 (SDSS) gikonje cyahinduwe super duplex stainless steel 2507 (SDSS) mu gihe cyo guhinduka kwayo mu bushyuhe. Nubwo mikorosikopi ya X-ray photoelectron yagaragaje ko urwego rw’ubushyuhe bwa Cr2O3 rungana, imikorere ya passivation ya SDSS ikozwe muri cold rolled yari mibi bitewe n’uko ibirwa bya nanois bya Fe3+ bikungahaye ku urwego rwa oxide rwa Fe/Cr. Ubu bumenyi bwa atome butanga ubumenyi bwimbitse ku bijyanye n’isenyuka ry’icyuma gitagira umugese kandi byitezwe ko bizafasha kurwanya ingese y’ibyuma bisa nabyo bifite alloy nyinshi.
Kuva aho icyuma gishyushye cyavumbuwe, ubushobozi bwo kurwanya ingese bwa ferrochrome buterwa na chromium, ikora oxyde/oxyhydroxides zikomeye kandi ikagaragaza imyitwarire yo kudakora mu bidukikije byinshi. Ugereranyije n'ibyuma bisanzwe (austenitic na ferritic) bita "ferritic" 1, 2, 3, "super duplex stainless steels" (SDSS) bifite ubushobozi bwo kurwanya ingese neza kandi bifite ubushobozi bwiza bwo gukora. Ingufu nyinshi za mashini zituma habaho imiterere yoroheje kandi mito. Mu buryo bunyuranye, SDSS ihendutse ifite ubushobozi bwo kurwanya ingese zo mu mwobo n'imyenge, bigatuma iramba, bityo ikarushaho gukoreshwa mu kugenzura umwanda, ibikoresho bya shimi, n'inganda za peteroli na gaze zo mu mazi4. Ariko, ubushyuhe buke bwo gutunganya ubushyuhe n'imiterere mibi bibangamira ikoreshwa ryabyo mu buryo bufatika. Kubwibyo, SDSS irahindurwa kugira ngo inoze imikorere yavuzwe haruguru. Urugero, ihinduka rya Ce ryashyizwe muri SDSS 2507 (Ce-2507) rifite azote nyinshi6,7,8. Ikintu cy’ubutaka budakunze kuboneka (Ce) ku gipimo gikwiye cya 0.08 wt.% gifite ingaruka nziza ku miterere ya DSS, kuko cyongera ubushobozi bwo kunoza ibinyampeke no gukomera k’umupaka w’ibinyampeke. Ubudahangarwa bw’ibinyampeke n’ubudahangarwa, imbaraga zo gukurura no gutanga umusaruro, hamwe n’ubushobozi bwo gukora bushyuha nabyo birarushaho kuba byiza9. Azote nyinshi ishobora gusimbura ingano ihenze ya nikeli, bigatuma SDSS irushaho kuba nziza10.
Vuba aha, SDSS yahinduwe plastike mu bushyuhe butandukanye (cryogenic, bukonje n'ubushyuhe) kugira ngo igere ku miterere myiza ya mekanike6,7,8. Ariko, ubushobozi bwiza bwo kurwanya ingese bwa SDSS bitewe no kuba hari agace gato ka oxide hejuru y'ubutaka bugirwaho ingaruka n'ibintu byinshi nko kuba hari itandukaniro risanzwe bitewe no kuba hari ibice bitandukanye bifite imipaka itandukanye y'ingano, imiterere idakenewe n'uburyo butandukanye bwo gusubiza. 7. Kubwibyo, kwiga imiterere ya microscope ya bene ayo mafilime kugeza ku rwego rw'imiterere ya elegitoroniki biba ingenzi cyane kugira ngo dusobanukirwe ingese ya SDSS kandi bisaba ubuhanga bugoye bwo kugerageza. Kugeza ubu, uburyo bworoshye bwo kwitabwaho n'ubuso nka Auger electron spectroscopy11 na X-ray photoelectron spectroscopy12,13,14,15 na mikroskopi ikomeye ya X-ray photoemission (HAX-PEEM)16 muri rusange bwananiwe kubona itandukaniro rya shimi mu bice bimwe by'ubuso. imiterere ya shimi y'ikintu kimwe ahantu hatandukanye mu mwanya wa nanoscale. Ubushakashatsi bwinshi buherutse bwagaragaje isano iri hagati ya okiside ya chromium n’imyitwarire ya corruption yagaragaye mu byuma bita austenitic stainless steels17, martensitic steels18 na SDSS19,20. Ariko, ubu bushakashatsi bwibanze cyane ku ngaruka za heterogeneity ya Cr (urugero, Cr3+ oxidation state) ku kurwanya corruption. Ubudasa bw’inyuma mu miterere ya okiside y’ibintu bushobora guterwa n’ibintu bitandukanye bifite ibintu bimwe bigize, nka okiside y’icyuma. Ibi bintu, byarazwe ingano ntoya bitewe no kuvurwa na thermomechanical, biri hafi cyane, ariko bitandukanye mu miterere n’imiterere ya okiside16,21. Kubwibyo, kugira ngo hamenyekane imiterere ya okiside no gucika kw’ibice bikurikira, ni ngombwa gusobanukirwa ubwinshi bw’ubuso ku rwego rwa mikorosikopi. Nubwo hari ibi bisabwa, ibipimo by’imibare nk’ubwinshi bw’ubudasa bw’inyuma mu kurwanya corruption, cyane cyane kuri Fe ku gipimo cya nano- na atome, biracyahari, kandi isano yabyo n’ubwinshi bw’ubudasa ntiramenyekana. Kugeza vuba aha, imiterere y’ibinyabutabire by’ibintu bitandukanye, nka Fe na Ca22, ku byuma byapimwe mu buryo bw’ingano hakoreshejwe mikorosikopi yoroshye ya X-ray photoelectron (X-PEEM) mu bikoresho by’imirasire ya nanoscale synchrotron. Iyo X-PEEM ihujwe na spectroscopy yoroshye gukoresha X-ray absorption spectroscopy (XAS), ifasha gupima XAS ifite ubushobozi bwo kureba ahantu hanini no kureba ahantu hanini, itanga amakuru y’ibinyabutabire ku miterere y’ibintu n’imiterere yabyo hamwe n’ubushobozi bwo kureba ahantu kugeza kuri nanometero makumyabiri n’eshatu. Uku kureba spectromicroscope kw’intangiriro y’ibintu byoroshya kureba ibinyabutabire byo mu gace kandi bishobora kwerekana impinduka mu buryo bw’ibinyabutabire mu mwanya w’icyuma kitari cyasuzumwa mbere.
Ubu bushakashatsi bwongera inyungu za PEEM mu kubona itandukaniro rya shimi kuri nanoscale kandi butanga uburyo bwo gusesengura ubuso bwa atome mu gusobanukirwa imyitwarire ya corruption ya Ce-2507. Bukoresha uburyo bwa K-means24 chemiquet buhuriweho kugira ngo bugaragaze uburinganire bw'ibinyabutabire ku isi (hetero) by'ibintu biyigize, aho imiterere ya shimi igaragazwa mu buryo bw'ibarurishamibare. Bitandukanye na corruption yatangijwe no kwangirika kwa chromium oxide film mu buryo busanzwe, corruption nke no kugabanuka kwa corruption resistance muri iki gihe biterwa n'ibirwa bya nanois bya Fe3+ biri hafi y'urwego rwa oxide rwa Fe/Cr, bishobora kuba imiterere yo kurinda. Oxyde yangiza firime ifite utudomo kandi igatera corruption.
Imyitwarire ya SDSS 2507 yangiritse yabanje gusuzumwa hakoreshejwe ibipimo bya elegitoroniki. Ku ishusho ya 1 yerekana imiyoboro ya Nyquist na Bode ku bipimo byatoranijwe mu gisubizo cy’amazi cya aside (pH = 1) cya FeCl3 ku bushyuhe bw’icyumba. Electrolyte yatoranijwe ikora nk'ikintu gikomeye gitanga ogisijeni, kigaragaza imiterere ya firime yo kwangirika. Nubwo ibikoresho bitanyuze mu mwobo uhamye ku bushyuhe bw’icyumba, isesengura ryatanze ubumenyi ku bintu bishobora kwangirika ndetse no kwangirika nyuma yaho. Urusobe rw’amazi (Ishusho ya 1d) rwakoreshejwe kugira ngo ruhuze na spectroscopy ya impedance ya elegitoroniki (EIS), kandi ibisubizo bijyanye n’ibyo bipimo bigaragazwa mu mbonerahamwe ya 1. Uduce tw’amazi tutuzuye tugaragara mu bipimo byavuwe n’ibishyushye, mu gihe utwuma tw’amazi dukonje tugaragara mu duce twakonje (Ishusho ya .1b). Muri spectroscopy ya EIS, uburebure bw’urusobe rw’uruziga bushobora gufatwa nk’ubudahangarwa bwa polarization (Rp)25,26. Ingano ya Rp y'inzira y'indege yavuwe mu buryo bw'umuti muri Imbonerahamwe ya 1 ni hafi 135 kΩ cm–2, icyakora, agaciro k'inzira y'indege ishyushye n'ifite icyuma gikonje ni gake cyane, 34.7 na 2.1 kΩ cm–2, uko bikurikirana. Uku kugabanuka gukomeye kwa Rp bigaragaza ingaruka mbi zo kwangirika kwa pulasitiki ku kudakora no kudakora neza kw'ingufu, nk'uko bigaragara muri raporo zabanje 27, 28, 29, 30.
Imbonerahamwe ya Nyquist, b, c Bode impedance na phase diagrams, na d bihuye na moderi z'urusobe rw'amashanyarazi, aho RS ari resistance ya electrolyte, Rp ari resistance ya polarization, na QCPE ni oxyde y'igice cy'urusobe cy'amashanyarazi gikoreshwa mu kwerekana capacitance idakwiye (n). Ibipimo bya EIS bikorerwa kuri open circuit potential.
Ibipimo bya buri gihe bigaragazwa muri Bode plot, hamwe n'ikibaya kiri mu rugero rwo hejuru rw'umuvuduko ugaragaza electrolyte resistance RS26. Uko umuvuduko ugabanuka, impedance iriyongera kandi inguni y'igice cya negative iraboneka, bigaragaza ko capacitance ari yo iganza. Inguni y'igice iriyongera, igumana ntarengwa ku rugero rwagutse rw'umuvuduko, hanyuma ikagabanuka (Ishusho ya 1c). Ariko, muri ibyo bihe uko ari bitatu, iyi ntarengwa iracyari munsi ya 90°, igaragaza imyitwarire idakwiye ya capacitive bitewe no gukwirakwira kwa capacitive. Bityo, QCPE constant phase element (CPE) ikoreshwa mu kwerekana ikwirakwizwa rya capacitance interfacial rituruka ku guhindagurika k'ubuso cyangwa kutagira aho bihuriye, cyane cyane ku gipimo cya atome, geometry ya fractal, porosity ya electrode, ubushobozi butari bumwe, na geometry ifite imiterere ya electrodes31,32. CPE impedance:
aho j ari umubare wiyumvirwa naho ω ikaba ari umurongo w’ingufu. QCPE ni umurongo uhoraho wigenga ujyanye n’agace gafunguye neza k’amashanyarazi. n ni umubare w’imbaraga udafite ingano usobanura ihinduka rya capacitor uvuye kuri capacitance ikwiye, ni ukuvuga ko iyo n yegereye 1, CPE yegereye capacitive gusa, mu gihe iyo n yegereye zeru, isa nkaho irwanya. Ihindagurika rito rya n, hafi ya 1, rigaragaza imyitwarire idakwiye ya capacitive y’ubuso nyuma y’ibizamini bya polarization. QCPE ya SDSS ikora neza iri hejuru cyane ugereranyije na bagenzi bayo, bivuze ko ubwiza bw’ubuso budahuje neza.
Bijyanye n'imiterere myinshi yo kurwanya ingese mu byuma bitagira umugese, Cr nyinshi ya SDSS muri rusange ituma SDSS irwanya ingese neza bitewe n'uko hari agace ka okiside gakingira ingese ku buso17. Utwo duce dukingira ingese akenshi tuba twinshi muri okiside za Cr3+ na/cyangwa hydroxides, cyane cyane hamwe na Fe2+, okiside za Fe3+ na/cyangwa hydroxides (okiside)33. Nubwo ubuso bungana, urwego rwa okiside rugabanya ingese, kandi nta gice cyagaragaye gicika hakurikijwe ibipimo bya mikorosikopi6,7, imiterere ya SDSS ishyushye n'ikora ikonje iratandukanye, bityo inyigo yimbitse ku miterere y'imiterere y'icyuma ni ngombwa kugira ngo icyuma gihinduke.
Imiterere y’icyuma kitagira umugese yakozweho ubushakashatsi ku mibare hakoreshejwe imirasire ya X-rays y’imbere n’iy’imbaraga nyinshi ya synchrotron (Ishusho y’inyongera 1, 2). Isesengura rirambuye riratangwa mu makuru y’inyongera. Nubwo hari ubwumvikane rusange ku bwoko bw’igice kinini, itandukaniro mu bice by’igice kinini byabonetse, byavuzwe mu mbonerahamwe y’inyongera 1. Iri tandukaniro rishobora guterwa n’ibice by’igice bitagira umugese ku buso no mu bunini, bigizweho ingaruka n’ubujyakuzimu butandukanye bwo kubona imirasire ya X-ray (XRD). ) hamwe n’amasoko atandukanye y’ingufu za fotoni z’impanuka34. Ibice byinshi bya austenite mu bipimo bikonje byagenwe na XRD bivuye ku isoko rya laboratwari bigaragaza ko habaho kudakora neza hanyuma bikarwanya ingese neza35, mu gihe ibisubizo nyabyo kandi by’imibare bigaragaza imiterere itandukanye mu bice by’igice. Byongeye kandi, kurwanya ingese kw’icyuma biterwa kandi n’urwego rwo kunoza ingese, kugabanuka kw’ingano y’ibice, kwiyongera kwa mikorobe n’ubucucike bw’ibice bibaho mu gihe cyo kuvurwa na thermomechanical36,37,38. Ingero zishyushye zagaragaje imiterere y’ibinyampeke byinshi, bigaragaza ko ari ibinyampeke bingana na mikoroni, mu gihe impeta zoroshye zagaragaye mu ngero zikonje (Ishusho y’inyongera ya 3) zagaragazaga ko ibinyampeke byarushijeho kunozwa cyane mu bushakashatsi bwakozwe mbere. Ibi byagombye gutuma filime idakora neza kandi ikiyongera cyo kudakora neza. Ubucucike bwinshi bwo gutandukana bukunze kujyana no kudakora neza kw’ibinyampeke, ibyo bikaba bihuye neza n’ibipimo by’amashanyarazi.
Impinduka mu miterere y’ibinyabutabire bya microdomains z’ibintu by’ingenzi byigwaga neza hakoreshejwe X-PEEM. Nubwo hari ibindi bintu byinshi bivangavanze, Cr, Fe, Ni na Ce39 byatoranyijwe hano, kubera ko Cr ari ingenzi mu gukora filime idakora, Fe ni ingenzi mu byuma, na Ni yongera passivation kandi ikaringaniza phase ya ferrite-austenitic. Imiterere n’impinduka ni intego ya Ce. Mu gutunganya ingufu z’umuraba wa synchrotron, XAS yafashe imiterere y’ingenzi ya Cr (inkombe ya L2.3), Fe (inkombe ya L2.3), Ni (inkombe ya L2.3), na Ce (inkombe ya M4.5) uhereye hejuru. -2507 SDSS. Isesengura ry’amakuru rikwiye ryakozwe hashyirwamo gupima ingufu hamwe n’amakuru yasohotse (urugero: XAS kuri Fe L2, imbavu 340,41).
Ku ishusho ya 2, ishusho ya 2 igaragaza amashusho ya X-PEEM y’ibikoresho bishyushye (Ishusho ya 2a) n’ibikonje (Ishusho ya 2d) Ce-2507 SDSS hamwe n’impande za XAS Cr na Fe L2,3 zijyanye nabyo ku myanya yagenwe ukwayo. Impande ya L2,3 XAS isuzuma imiterere ya 3d idafite ibikoresho bya electron nyuma yo gusohora foto ku rugero rwa 2p3/2 (L3 edge) na 2p1/2 (L2 edge) spin-orbit. Amakuru yerekeye imiterere ya valence ya Cr yabonetse mu isesengura rya X-ray diffraction ku mpande za L2,3 ku ishusho ya 2b, d. Igereranya ry’ibikubiye ku murongo. 42, 43 ryagaragaje ko imisozi ine A (578.3 eV), B (579.5 eV), C (580.4 eV), na D (582.2 eV) byagaragaye hafi y’impande za L3, bigaragaza ioni za octahedral Cr3+ ions, Cr2O3 ijyanye na zo. Ibipimo by'igerageza bihuye n'ibipimo by'imitekerereze, nk'uko bigaragara ku mabara ya b na e, yakuwe mu mibare myinshi y'ibipimo bya kristu ku rubuga rwa Cr L2.3 hakoreshejwe kristu ya 2.0 eV44. Ubuso bwombi bwa SDSS ishyushye n'ifite imiterere ikonje butwikiriwe n'urwego rumwe rwa Cr2O3.
Ishusho y'ubushyuhe ya X-PEEM SDSS ishyushye ihuye n'inkombe b Cr L2.3 n'inkombe c Fe L2.3, d Ishusho y'ubushyuhe X-PEEM ya SDSS ikonje ihuye n'inkombe e Cr L2.3 na f Fe L2.3 by'uruhande (e). Imiterere ya XAS yashushanyijwe ahantu hatandukanye h'ahantu hagaragara ku mashusho y'ubushyuhe (a, d) n'imirongo y'umuhondo irimo utudomo muri (b) na (e) igaragaza imiterere ya XAS ya Cr3+ ifite agaciro ka kristu ka 2.0 eV. Ku mashusho ya X-PEEM, hakoreshwa uburyo bwo gushyuha kugira ngo hongerwe uburyo bwo gusoma amashusho, aho amabara kuva ku bururu kugeza ku mutuku ahuye n'ubukana bw'imirasire ya X (kuva hasi kugeza hejuru).
Uko ibi bintu by'icyuma bihagaze kose, imiterere ya shimi yo kongeramo ibintu bya Ni na Ce kuri ibyo bice byombi yagumye ari imwe. Ishusho y'inyongera. Ku ishusho ya 5-9 herekanwa amashusho ya X-PEEM n'ibipimo bya XAS bihuye na Ni na Ce ku myanya itandukanye ku buso bw'ibipimo bishyushye n'ibikonje. Ni XAS igaragaza imiterere ya oxidation ya Ni2+ ku buso bwose bwapimwe bw'ibipimo bishyushye n'ibikonje (Ibiganiro by'inyongera). Ni ngombwa kumenya ko ku bipimo bishyushye, ikimenyetso cya XAS cya Ce ntikigaragara, mu gihe imiterere ya Ce3+ y'ibipimo bikonje igaragara ahantu hamwe. Kubona utudomo twa Ce mu bipimo bikonje byagaragaje ko Ce ibaho ahanini mu buryo bw'imvura.
Muri SDSS yahinduwe n’ubushyuhe, nta mpinduka mu miterere ya XAS yagaragaye ku nkengero za Fe L2.3 (Ishusho ya 2c). Ariko, nk’uko bigaragara ku ishusho ya 2f, matrix ya Fe ihindura imiterere yayo ya shimi mu buryo bwa mikorosikopi ku ngingo zirindwi zatoranijwe mu buryo butunguranye muri SDSS ikonje. Byongeye kandi, kugira ngo haboneke igitekerezo nyacyo cy’impinduka mu miterere ya Fe ahantu hatoranijwe ku ishusho ya 2f, hakozwe inyigo ku buso bw’aho hantu (Ishusho ya 3 n’Ishusho y’inyongera ya 10) aho uturere duto tw’uruziga twatoranijwe. Imiterere ya XAS y’inkombe za Fe L2,3 za sisitemu za α-Fe2O3 na okiside za Fe2+ octahedral yashushanyijwe hakoreshejwe imibare ya crystal fields nyinshi hakoreshejwe crystal fields ya 1.0 (Fe2+) na 1.0 (Fe3+)44. Tubona ko α-Fe2O3 na γ-Fe2O3 bifite symmetries zitandukanye zo mu gace45,46, Fe3O4 ifite uruvange rwa Fe2+ na Fe3+,47, na FeO45 nk'umusemburo wa Fe2+ uhuza (3d6). Tubona ko α-Fe2O3 na γ-Fe2O3 bifite symmetries zitandukanye zo mu gace45,46, Fe3O4 ifite uruvange rwa Fe2+ na Fe3+,47, na FeO45 nk'umusemburo wa Fe2+ uhuza (3d6) ku buryo bwemewe.Menya ko α-Fe2O3 na γ-Fe2O3 bifite symmetries zitandukanye zo mu gace45,46, Fe3O4 ihuza Fe2+ na Fe3+,47 na FeO45 mu buryo bwa okiside ivanze Fe2+ (3d6).Menya ko α-Fe2O3 na γ-Fe2O3 bifite symmetries zitandukanye zo mu gace45,46, Fe3O4 ifite uruvange rwa Fe2+ na Fe3+,47 na FeO45 ikora nk'umusemburo wa Fe2+ (3d6). Iyoni zose za Fe3+ muri α-Fe2O3 zifite imyanya ya Oh gusa, mu gihe γ-Fe2O3 ikunze kugaragazwa nka Fe3+ t2g [Fe3+5/3V1/3]eg O4 spinel hamwe n'impapuro z'icyuho mu myanya y'icyuho. Kubwibyo, iyoni za Fe3+ muri γ-Fe2O3 zifite imyanya ya Td na Oh. Nkuko byavuzwe mu kazi kabanje, nubwo ikigereranyo cy'ubukana bw'ibi byombi gitandukanye, ikigereranyo cyabyo cy'ubukana urugero/t2g ni ≈1, mu gihe muri iki gihe ikigereranyo cy'ubukana cyagaragaye urugero/t2g kiri hafi 1. Ibi bikuraho ko hari Fe3+ gusa muri iki kibazo. Urebye urugero rwa Fe3O4 hamwe n’uruvange rwa Fe2+ na Fe3+, birazwi ko ikimenyetso cya mbere gito (gikomeye) mu nkengero za L3 za Fe kigaragaza ko nta kintu kinini (kinini) kiri muri t2g. Ibi bireba Fe2+ (Fe3+), bigaragaza ko ikimenyetso cya mbere cyerekana ko hari ukwiyongera kw'ibikubiye muri Fe2+47. Ibi bisubizo bigaragaza ko Fe2+ na γ-Fe2O3, α-Fe2O3 na/cyangwa Fe3O4 byiganje ku buso bukonje bw'ibivanze.
Amashusho ya electron y'ubushyuhe ya fotoegisiyo yagutse ya spectra ya (a, c) na (b, d) ya XAS ku nkengero za Fe L2,3 mu myanya itandukanye y'ahantu mu turere twatoranijwe twa 2 na E mu ishusho ya 2d.
Amakuru yabonetse mu bushakashatsi (Ishusho ya 4a n'Ishusho y'inyongera ya 11) yashushanyijwe kandi agereranywa n'ay'ibinyabutabire 40, 41, 48. Muri make, ubwoko butatu butandukanye bwa spectra ya Fe L-edge XAS yabonetse mu bushakashatsi (XAS-1, XAS-2 na XAS-3: Ishusho ya 4a) yabonetse ahantu hatandukanye mu buryo bw'ikirere. By'umwihariko, spectra isa na 2-a (yitiriwe XAS-1) mu Ishusho ya 3b yagaragaye mu karere kose gafite akamaro, hagakurikiraho spectra ya 2-b (yanditseho XAS-2), mu gihe spectra isa na E-3 yagaragaye mu Ishusho ya 3d (yitiriwe XAS-3) yagaragaye ahantu hamwe na hamwe. Ubusanzwe, ibipimo bine bikoreshwa mu kumenya imiterere ya valence iri mu gipimo cya probe: (1) Ibiranga spectra ya L3 na L2, (2) imyanya y'ingufu y'ibiranga L3 na L2, (3) itandukaniro ry'ingufu za L3-L2, (4) igipimo cy'ubukana bwa L2 /L3. Dukurikije uko byagaragaye mu buryo bw'amaso (Ishusho ya 4a), ibice bitatu bya Fe, ari byo Fe0, Fe2+, na Fe3+, biri ku buso bwa SDSS yizwe. Igipimo cy'ubukana cyabazwe L2/L3 cyanagaragaje ko ibice bitatu byose biriho.
a Habonetse amakuru atatu atandukanye yo mu bushakashatsi (imirongo ikomeye XAS-1, XAS-2 na XAS-3 bihuye na 2-a, 2-b na E-3 ku ishusho ya 2 n'ishusho ya 3) ugereranije na XAS yakozwe mu buryo bwa XAS, octahedrons Fe2+, Fe3+, agaciro k'umurima wa kristalo wa 1.0 eV na 1.5 eV, uko bikurikirana, b–d Hapimwe amakuru yo mu bushakashatsi (XAS-1, XAS-2, XAS-3) n'amakuru ya LCF ahuye nayo (umurongo w'umukara ukomeye), kandi hagereranywa spectra ya XAS-3 na Fe3O4 (imiterere ivanze ya Fe) na Fe2O3 (Fe3+ y'umwimerere).
Uburyo bwo guhuza umurongo (LCF) bw’ibipimo bitatu 40,41,48 bwakoreshejwe kugira ngo harebwe imiterere ya okiside y’icyuma. LCF yashyizwe mu bikorwa kuri spectra eshatu zatoranijwe za Fe L-edge XAS zigaragaza itandukaniro rikomeye, ari zo XAS-1, XAS-2 na XAS-3, nk'uko bigaragara ku Ishusho ya 4b–d. Ku bijyanye n’ibikoresho bya LCF, 10% Fe0 yatekerejweho mu bihe byose bitewe n’agace gato twabonye mu makuru yose ndetse n’uko icyuma cya ferrous ari cyo gice cy’ingenzi cy’icyuma. Mu by’ukuri, ubujyakuzimu bw’igeragezwa bwa X-PEEM kuri Fe (~6 nm)49 buruta ubunini bw’urwego rwa oxidation bugereranyijwe (bugera kuri 4 nm gato), butuma hamenyekana ikimenyetso kiva kuri matrix y’icyuma (Fe0) munsi y’urwego rwa passivation. Mu by’ukuri, ubujyakuzimu bw’igeragezwa bwa X-PEEM kuri Fe (~6 nm)49 buruta ubunini bw’urwego rwa oxidation bugereranyijwe (bugera kuri 4 nm gato), butuma hamenyekana ikimenyetso kiva kuri matrix y’icyuma (Fe0) munsi y’urwego rwa passivation. Действительно, Кнаная глубина X-PEEM для Fe (~ 6 нм) 49 больше, чем предполагаемая толщина слоя окисления (немного> 4 нм), что позволяет обнаружить у от железной матрицы (Fe0) Mu by’ukuri, ubujyakuzimu bwa probe X-PEEM kuri Fe (~6 nm)49 buruta ubunini bw’urwego rwa oxidation (burenze gato 4 nm), bituma bishoboka kubona ikimenyetso kiva kuri matrix y’icyuma (Fe0) munsi y’urwego rwa passivation.Mu by’ukuri, X-PEEM ibona Fe (~6 nm)49 yimbitse kurusha ubunini bw’urwego rwa okiside (irenga gato 4 nm), bigatuma hamenyekana ibimenyetso bivuye kuri matrix y’icyuma (Fe0) munsi y’urwego rwa passivation. Hakozwe uburyo butandukanye bwo guhuza Fe2+ na Fe3+ kugira ngo haboneke igisubizo cyiza gishoboka ku makuru yabonetse mu bushakashatsi. Ku ishusho ya 4b, hagaragazwa uburyo Fe2+ na Fe3+ bihurirana muri XAS-1 spectrum, aho ibipimo bya Fe2+ na Fe3+ biri hafi, hafi 45%, bigaragaza imiterere ya okiside ivanze ya Fe. Mu gihe kuri XAS-2 spectrum, ijanisha rya Fe2+ na Fe3+ riba ~30% na 60%, uko bikurikirana. Ibipimo bya Fe2+ biri hasi ugereranyije n’ibya Fe3+. Ikigereranyo cya Fe2+ na Fe3 cya 1:2 bivuze ko Fe3O4 ishobora kuboneka ku gipimo kimwe cya iyoni za Fe. Byongeye kandi, kuri XAS-3 spectrum, ijanisha rya Fe2+ na Fe3+ ryahindutse rigera kuri ~10% na 80%, bigaragaza ko Fe2+ yahindutse cyane muri Fe3+. Nkuko byavuzwe haruguru, Fe3+ ishobora kuva kuri α-Fe2O3, γ-Fe2O3 cyangwa Fe3O4. Kugira ngo dusobanukirwe isoko ishoboka cyane ya Fe3+, XAS-3 spectra zishushanyije hamwe n’ibipimo bitandukanye bya Fe3+ ku Gishushanyo cya 4e bigaragaza ko bisa n’ibipimo byombi iyo hatekerejwe ku Gipimo cya B. Ariko, ubukana bw’urutugu (A: kuva kuri Fe2+) n’igipimo cy’ubukana B/A bigaragaza ko igipimo cya XAS-3 kiri hafi ariko kitari kimwe n’icya γ-Fe2O3. Ugereranyije na bulk γ-Fe2O3, ubukana bwa Fe 2p XAS bw’igipimo cya A SDSS buri hejuru gato (Igishushanyo cya 4e), bigaragaza ubukana bwa Fe2+ buri hejuru. Nubwo imiterere ya XAS-3 isa n’iya γ-Fe2O3, aho Fe3+ iboneka mu myanya ya Oh na Td, kumenya imiterere itandukanye ya valence no guhuza gusa hakoreshejwe uburebure bwa L2,3 cyangwa igipimo cy’ubukana bwa L2/L3 biracyari ikibazo. Iyi ni ingingo ikunze kuganirwaho bitewe n’ubukana bw’ibintu bitandukanye bigize imiterere ya nyuma41.
Uretse itandukaniro rya spectral ry’imiterere y’ibinyabutabire mu turere twatoranijwe twavuzwe haruguru, itandukaniro ry’ibinyabutabire ku isi hose ry’ibintu by’ingenzi Cr na Fe ryapimwe hashyirwa mu byiciro spectra zose za XAS zabonetse ku buso bw’icyitegererezo hakoreshejwe uburyo bwa K-means clustering. Imiterere ya Cr L yashyizweho ku buryo ikora amatsinda abiri meza akwirakwijwe mu buryo bushyushye n’akonje agaragara ku ishusho ya 5. Biragaragara ko nta mpinduka mu miterere y’aho hantu zagaragaye, kubera ko centroid ebyiri za XAS Cr spectra zisa cyane. Izi miterere ya spectral z’amatsinda abiri zisa hafi n’izijyanye na Cr2O342, bivuze ko urwego rwa Cr2O3 rukwirakwijwe neza kuri SDSS.
itsinda ry'uturere twa K-means L-edge Cr, b bihuye na XAS centroids. Ibisubizo by'igereranya rya K-means X-PEEM rya SDSS ikonje: c c cles of K-means edge regions of Cr L2,3 and d bihuye na XAS centroids.
Kugira ngo hagaragazwe ikarita y’inkombe ya FeL igoye kurushaho, amatsinda ane na atanu yakozwe neza hamwe na centroids zijyanye nayo (ibipimo bya spectral) bikoreshwa ku bipimo bishyushye n’ibikonje, uko bikurikirana. Kubwibyo, ijanisha (%) rya Fe2+ na Fe3+ rishobora kuboneka hakoreshejwe guhindura LCF igaragara ku Ishusho ya 4. Pseudo pseudo potential nk'uko byakozwe na Fe0 yakoreshejwe kugira ngo hagaragazwe ubusumbane bwa microchemical bwa filime ya oxide yo hejuru. Epseudo igereranywa n'itegeko ryo kuvanga,
aho \(\rm{E}_{\rm{Fe}/\rm{Fe}^{2 + (3 + )}}\) bingana na \(\rm{Fe} + 2e^ – \to\rm {Fe}^{2 + (3 + )}\), ari byo 0.440 na 0.036 V, uko bikurikirana. Uduce dufite ubushobozi buke dufite ingano nini y'ibinyabutabire bya Fe3+. Ingano y'ubushobozi mu gipimo cyangiritse mu bushyuhe ifite imiterere y'urwego ifite impinduka ntarengwa ya 0.119 V (Ishusho ya 6a, b). Uku gukwirakwiza ubushobozi bifitanye isano ya hafi n'imiterere y'ubuso (Ishusho ya 6a). Nta zindi mpinduka zijyanye n'umwanya zagaragaye mu gice cy'imbere cy'urumuri (Ishusho ya 6b). Ibinyuranye n'ibyo, ku ihuzwa rya okiside zitandukanye zifite ingano zitandukanye za Fe2+ na Fe3+ muri SDSS ikonje, imiterere idahuye y'ubushobozi buke ishobora kugaragara (Ishusho ya 6c, d). Okiside ya Fe3+ na/cyangwa hydroxides (okside) ni byo bigize ingese mu byuma kandi binyura muri ogisijeni n'amazi50. Muri iki gihe, bigaragara ko ibirwa bikungahaye kuri Fe3+ bikwirakwira mu gace runaka kandi bishobora gufatwa nk'ahantu hangiritse. Muri iki gihe, imiterere y'ubutaka bushobora gukwirakwira, aho kuba agaciro ka burundu k'ubushobozi, ishobora gufatwa nk'ikimenyetso cy'aho uturere dukoresha ingese dukorera51. Uku gukwirakwira kwa Fe2+ na Fe3+ ku buso bwa SDSS ikonje bishobora guhindura imiterere y'ibinyabutabire byo mu gace no gutanga ubuso bwiza mu gucika kw'ibumba rya okiside no kwangirika, bityo bigatuma icyuma kiri munsi yacyo kiguma cyangirika, bigatera ubusumbane bw'imbere. kandi bikagabanya imiterere y'uburinzi bw'urwego rudakora.
Amatsinda ya K-mean y’uturere tw’inkombe za Fe L2,3 hamwe na centroids za XAS zijyanye na a-c X-PEEM ishyushye na d-f SDSS ikonje. a, d K-means cluster plot iri hejuru y’ishusho ya X-PEEM. Ingano za pseudoelectrode (epseudo) zivugwa hamwe n’ibishushanyo bya K-means cluster. Umucyo w’ishusho ya X-PEEM nk’ibara riri ku Ishusho ya 2 ujyanye neza n’ubukana bwa X-ray.
Kuba Cr imwe ariko imiterere itandukanye ya Fe itera inkomoko itandukanye yo gucika kw'urumuri rwa okiside no kwangirika mu miterere ya Ce-2507 ishyushye n'ikonje. Iyi miterere ya Ce-2507 ishyushye irazwi cyane. Ku bijyanye no kurema okiside na hydroxide za Fe mu kirere cyo mu kirere, muri iki gitabo havugwamo ingaruka zidafite aho zibogamiye:
Hashingiwe ku gupima X-PEEM, iyi reaction yavuzwe haruguru yabayeho mu bihe bikurikira. Urutugu ruto rujyanye na Fe0 rufitanye isano n'icyuma kiri munsi yacyo. Ihinduka rya Fe y'icyuma n'ibidukikije rituma habaho urwego rwa Fe (OH)2 (ikigereranyo (5)), byongerera ikimenyetso cya Fe2+ muri XAS y'inkombe ya L ya Fe. Kugaragara mu mwuka igihe kirekire bizatuma habaho Fe3O4 na/cyangwa Fe2O3 oxydes nyuma ya Fe(OH)252,53. Ubwoko bubiri bwa Fe ihamye, Fe3O4 na Fe2O3, bushobora no kubaho mu urwego rurinda Cr3+ rwinshi, aho Fe3O4 ikunda imiterere imwe kandi ifatanye. Kubaho kwabyo byombi bivamo imiterere ivanze ya oxidation (XAS-1 spectrum). XAS-2 spectrum ihuye cyane na Fe3O4. Mu gihe XAS-3 spectra yagaragaye ahantu henshi yagaragaje ko yahindutse burundu muri γ-Fe2O3. Kubera ko imirasire ya X idapfunyitse ifite ubujyakuzimu bwo kwinjira bwa nm 50, ikimenyetso gituruka ku gice cyo hasi gitanga ubukana bwinshi bw'agasongero ka A.
Ishusho ya XRD igaragaza ko igice cya Fe muri filime ya oxide gifite imiterere y’icyiciro, ihuzwa n’icyiciro cya oxide cya Cr. Bitandukanye n’uburyo corruption iterwa no kudahuza kwa Cr2O317, nubwo Cr2O3 iri mu cyiciro kimwe muri ubu bushakashatsi, muri uru rubanza hagaragaye ko hari ubudahangarwa buke bwo kwangirika, cyane cyane ku ngero zikonje. Imyitwarire yagaragaye ishobora kumvikana nk’ubusumbane bw’imiterere ya chemical oxidation y’icyiciro cyo hejuru (Fe) igira ingaruka ku mikorere ya corruption. Kwimura buhoro kwa iyoni z’icyuma cyangwa ogisijeni mu gice cy’urukuta bitewe na stoichiometry imwe y’icyiciro cyo hejuru (Fe oxide) n’icy’inyuma (Cr oxide)52,53 bituma habaho imikoranire myiza (gufatana) hagati yabyo. Ibi, nabyo birushaho kunoza ubudahangarwa bwo kwangirika. Kubwibyo, stoichiometry ihoraho, ni ukuvuga imiterere imwe ya oxidation ya Fe, ni byiza kuruta impinduka zitunguranye za stoichiometric. SDSS yahinduwe mu bushyuhe ifite ubuso bumwe kandi ifite urwego rwo kurinda, rutanga ubudahangarwa bwiza bwo kwangirika. Ariko, kuri SDSS ikonje, kuba hari ibirwa byinshi bya Fe3+ munsi y’urwego rurinda byangiza ubusugire bw’ubuso kandi bigatera kwangirika kwa galvanic ku gice cyo hafi, bigatuma Rp (Imbonerahamwe ya 1) igabanuka mu buryo bwa EIS spectra no kwangirika kwayo. Kubwibyo, ibirwa bikwirakwijwe mu gace bikungahaye kuri Fe3+ bitewe no kwangirika kwa pulasitiki bigira uruhare runini mu mikorere yo kwangirika, ibi bikaba ari intambwe ikomeye muri iki gikorwa. Kubwibyo, ubu bushakashatsi bugaragaza spectromicrographe zerekana kugabanuka k’kwangirika kwa pulasitiki bitewe no kwangirika kwa pulasitiki ku bipimo bya SDSS byizwe.
Byongeye kandi, nubwo ikoreshwa ry’ibintu bidakunze kuboneka mu byuma bikozwe mu buryo bwa dual phase rikora neza, uburyo iki kintu cyongeweho hamwe n’icyuma gikozwe mu buryo bwa corruption ntabwo bushoboka bitewe n’uko byagaragaye muri microscopy. Ikimenyetso cya Ce (kuri XAS M-edge) kigaragara ahantu hake gusa mu gihe cyo gukonja, ariko kikabura mu gihe cyo gushyuha kwa SDSS, bigaragaza ko Ce iri mu gice cy’icyuma aho kuba ikoreshwa mu buryo bumwe. Nubwo imiterere ya SDSS idahinduka6,7, kuba hari REE bigabanya ingano y’ibintu bikubiye muri icyo gice kandi bikekwa ko bigabanya imyanda aho ikomoka54.
Mu gusoza, iki gikorwa kigaragaza ingaruka z'ubusumbane bw'ubuso ku kwangirika kwa 2507 SDSS yahinduwe na cerium binyuze mu gupima ingano y'ibinyabutabire mu bice bya nanoscale. Twasubije ikibazo cy'impamvu icyuma kitagira umugese cyangirika nubwo cyasizwe n'urwego rwa okiside rurinda twiga ku buryo burambuye imiterere ya microstructure, imiterere y'ibinyabutabire ku buso no gutunganya ibimenyetso hakoreshejwe uburyo bwa K-means clustering. Byaragaragaye ko ibirwa bikungahaye kuri Fe3+, harimo n'imikoranire yabyo ya octahedral na tetrahedral mu miterere ya Fe2+/Fe3+, ari isoko yo kwangirika kwa oxide film ndetse n'isoko yo kwangirika kwa SDSS ikonje. Ibirwa bya Nanois byiganjemo Fe3+ bituma habaho ubudahangarwa bubi bwo kwangirika ndetse no mu gihe hari urwego ruhagije rwa Cr2O3 rudakora neza. Uretse iterambere ry'uburyo ryakozwe mu kugena ingaruka z'ubusumbane bw'ibinyabutabire bya nanoscale ku kwangirika, iki gikorwa cyitezweho gutera imbaraga mu mikorere y'ubuhanga kugira ngo hongerwe ubudahangarwa bw'ibyuma bitagira umugese mu gihe cyo gukora ibyuma.
Mu gutegura ingots za Ce-2507 SDSS zakoreshejwe muri ubu bushakashatsi, ibice bivanze, harimo na Fe-Ce master alloy ifunze imiyoboro y'icyuma cyuzuye, byashongeshejwe mu itanura rya kilometero 150 kugira ngo bikore icyuma gishongeshejwe hanyuma bisukwa mu byuma bicukurwa. Ibinyabutabire byapimwe (wt %) bigaragazwa mu mbonerahamwe y'inyongera ya 2. Ingot ibanza gushyuha ikorwamo ibice. Hanyuma icyuma cyashyizwemo ubushyuhe kuri 1050°C mu gihe cy'iminota 60 kugeza ku gisubizo gikomeye, hanyuma kikazimwa mu mazi kugeza ku bushyuhe bw'icyumba. Ingero zakoreweho ubushakashatsi zasuzumwe birambuye hakoreshejwe TEM na DOE kugira ngo zige ibyiciro, ingano y'ingano n'imiterere. Amakuru arambuye ku ngero n'uburyo bwo gukora aboneka mu zindi nkomoko6,7.
Gutunganya ingero z’ubushyuhe (φ10 mm × 15 mm) kugira ngo hakorwe ubushyuhe bushyushye hamwe n’umurongo w’ubushyuhe ujyanye n’icyerekezo cy’ubushyuhe bw’ibumba. Gukanda ubushyuhe bwinshi byakozwe ku muvuduko uhoraho uri hagati ya 0.01-10 s-1 ku bushyuhe butandukanye buri hagati ya 1000-1150 °C hakoreshejwe simulator y’ubushyuhe ya Gleeble-3800. Mbere yo gukanda, ingero zashyushywaga ku bushyuhe bwatoranijwe ku muvuduko wa 10 °C s-1 mu gihe cy’iminota 2 kugira ngo ubushyuhe buveho. Nyuma yo kugera ku bushyuhe bumwe, ingero zahinduwe ku gipimo nyacyo cya 0.7. Nyuma yo gukanda, zihita zizimwa n’amazi kugira ngo imiterere yazo ikomeze kuba mibi. Hanyuma ingero zikomeye zaciwe zihuye n’icyerekezo cyo gukanda. Muri ubu bushakashatsi bwihariye, twahisemo ingero yahinduwe ku bushyuhe kuri 1050 °C, 10 s-1 bitewe n’ubukomere bwinshi bwagaragaye kurusha izindi ngero7.
Ingero z’umuti ukomeye wa Ce-2507 w’ingano (80 × 10 × 17 mm3) zageragejwe ku mashini ya LG-300 ifite ibyiciro bitatu idahuza, yatanze imiterere myiza ya mekanike mu zindi nzego zose zo guhindura imiterere. 6. Igipimo cyo gukurura no kugabanya ubunini byari 0.2 m·s-1 na 5% kuri buri nzira, uko bikurikirana.
Imashini ya Autolab PGSTAT128N electrochemical workstation yakoreshejwe mu gupima SDSS hakoreshejwe electrochemical nyuma yo kugabanya ubunini bwa 90% (1.0 equivalent true strain) no gukanda bushyushye kugeza kuri 0.7 true strain kuri 1050 oC na 10 s-1. Iyi mashini ifite akantu k'amashanyarazi ka electrode eshatu gafite electrode yuzuye ya calomel nk'electrode reference, electrode ya grafiti counter, n'icyitegererezo cya SDSS nk'electrode ikora. Ingero zaciwemo silindari zifite umurambararo wa mm 11.3, ku mpande zazo insinga z'umuringa zashongeshejwe. Hanyuma icyitegererezo cyasutswemo epoxy resin, hasigara ahantu hafunguye 1 cm2 nk'electrode ikora (ubuso bwo hasi bw'icyitegererezo cy'uruziga). Witondere mu gihe cyo gukaraba epoxy no mu gihe cyo gukaraba no gukaraba nyuma kugira ngo wirinde gucika. Ubuso bw'aho bukorera burahanagurwa kandi bugasukurwa hakoreshejwe diyama polishing suspension ifite ingano ya mikoroni 1, isukurwa n'amazi ya distilled na ethanol hanyuma bugashyirwa mu kirere gikonje. Mbere yo gupima electrochemical, ingero zaciwe zashyizwe mu mwuka iminsi myinshi kugira ngo zikore filime karemano ya oxyde. Umuti w'amazi wa FeCl3 (6.0 wt.%), uhamye na HCl kuri pH = 1.0 ± 0.01, wakoreshejwe mu kwihutisha ingese y'icyuma kitagira umugese55, kuko uboneka ahantu hakomeye aho iyoni za chloride ziba zifite imbaraga zikomeye zo gusiga ogisijeni na pH nkeya nk'uko byagaragajwe na ASTM. Ibipimo ngenderwaho ni G48 na A923. Ingero zashyizwe mu gipimo cy'igerageza isaha 1 mbere yuko hafatwa ibipimo kugira ngo bigere ku rugero rwo hafi y'aho bitarahagarara. Ku bipimo by'umuti ukomeye, ibipimo bishyushye n'ibizingirwa bikonje, ingano y'impinduka zo gupima yari 1 × 105 ~ 0.1 Hz, naho ubushobozi bwo gufungura (OPS) bwari 5 mV, ari byo 0.39, 0.33, na 0.25 VSCE, uko bikurikirana. Buri kizamini cya elegitoroniki cy'icyitegererezo icyo ari cyo cyose cyasubiwemo nibura inshuro eshatu mu buryo bumwe kugira ngo amakuru ashobore kugaruka.
Ku bipimo bya HE-SXRD, ibyuma bya 1 × 1 × 1.5 mm3 by'urukiramende byapimwe ku murongo wa Brockhouse wiggler ufite ingufu nyinshi muri CLS, muri Kanada kugira ngo harebwe imiterere y'icyiciro56. Gukusanya amakuru byakozwe ku bushyuhe bw'icyumba muri geometry ya Debye-Scherrer cyangwa geometry yo gutwara. Uburebure bw'uburebure bwa X-rays bwapimwe kuri calibrant ya LaB6 ni 0.212561 Å, buhwanye na 58 keV, buri hejuru cyane y'ubwa Cu Kα (8 keV) busanzwe bukoreshwa nk'isoko ya X-ray yo muri laboratwari. Icyitegererezo gishyirwa ku ntera ya mm 740 uvuye ku gikoresho cyo gupima. Ingano yo gupima ya buri gipimo ni 0.2 × 0.3 × 1.5 mm3, bigenwa n'ingano y'imirasire n'ubugari bw'icyitegererezo. Buri makuru yakusanyijwe hakoreshejwe Perkin Elmer area detector, flat panel X-ray detector, 200 µm pixels, 40 × 40 cm2, hakoreshejwe igihe cyo kureba cy'amasegonda 0.3 n'amashusho 120.
Ibipimo bya X-PEEM by’uburyo bubiri bwatoranijwe byakorewe ku gice cya PEEM cy’umurongo wa Beamline MAXPEEM muri laboratwari ya MAX IV (Lund, Suwede). Ingero zateguwe kimwe n’izipimwa hakoreshejwe amashanyarazi. Ingero zateguwe zabitswe mu kirere iminsi myinshi kandi zikurwamo umwuka mu cyumba cy’ubushyuhe bwinshi mbere yo kunyuzwamo fotoni za synchrotron. Ingufu z’umuraba ziboneka hapimwa spectrum y’umusaruro wa ion kuva kuri N 1 s kugeza kuri 1\(\pi _g^ \ast\) y’agace gashyuha gafite hv = 401 eV muri N2 hamwe n’ingufu za fotoni zishingiye kuri E3/2.57. Ubushobozi bwa spectral bwatanze ΔE (ubugari bw’umurongo wa spectral) ~0.3 eV hejuru y’ingufu zapimwe. Kubera iyo mpamvu, igisubizo cy’ingufu za beamline cyagereranyijwe kuba E/∆E = 700 eV/0.3 eV > 2000 na flux ≈1012 ph/s hakoreshejwe monochromator yahinduwe ya SX-700 ifite Si 1200-line mm−1 grating kuri Fe 2p L2,3 edge, Cr 2p L2,3 edge, Ni 2p L2,3 edge, na Ce M4,5 edge. Kubera iyo mpamvu, igisubizo cy'ingufu za beamline cyagereranyijwe kuba E/∆E = 700 eV/0.3 eV > 2000 na flux ≈1012 ph/s hakoreshejwe monochromator yahinduwe ya SX-700 ifite Si 1200-line mm−1 grating kuri Fe 2p L2.3 edge, Cr 2p L2.3 edge, Ni 2p L2.3 edge, na Ce M4.5 edge. Таким кромка Cr 2p L2,3, кромка Ni 2p L2,3 и кромка Ce M4,5. Bityo, ubushobozi bwo kugaragaza ingufu z'umuyoboro w'imirasire bwapimwe nka E/∆E = 700 eV/0.3 eV > 2000 na flux ≈1012 f/s hakoreshejwe monochromator yahinduwe ya SX-700 ifite Si grating y'imirongo 1200 / mm kuri Fe edge 2p L2 ,3, Cr edge 2p L2.3, Ni edge 2p L2.3, na Ce edge M4.5.因此，光束线能量分辨率估计为 E / ΔE = 700 eV / 0.3 eV> 2000 和通量≈1012 ph / s 通过使用改进的 SX-700 单色器和 Si 1200 线 mm - 1 光栅用于 Fe 2p L2,3 边缘、 Cr 2p L2,3 边缘、 Ni 2p L2,3 边缘和 Ce M4,5 边缘。因此 ， 光束线 能量 分辨率 为 为 为 δe = 700 EV / 0.3 EV> 2000 和 ≈1012 PH / S 通过 改进 的 SX-700 单色器 和 SI 1200 线 mm-1 光栅 于 Fe 2P 2P 2P L2.3 边缘、 Cr 2p L2.3 边缘、 Ni 2p L2.3 边缘和 Ce M4.5Bityo, iyo ukoresheje monochromator yahinduwe ya SX-700 hamwe na grating ya Si ya 1200. 3, Cr edge 2p L2.3, Ni edge 2p L2.3 na Ce edge M4.5.Kwagura ingufu za photon mu ntambwe za 0.2 eV. Kuri buri ngufu, amashusho ya PEEM yafashwe hakoreshejwe uburyo bwa TVIPS F-216 CMOS detector ifite 2 x 2 binning fiber optic connection itanga pikseli 1024 × 1024 mu gice cyo kureba cya 20 µm. Igihe cyo kwerekana amashusho ni amasegonda 0.2, impuzandengo ya frame 16. Ingufu z'ishusho ya photoelectron zitoranywa mu buryo bwo gutanga ikimenyetso ntarengwa cya electron. Ibipimo byose bikorwa mu gihe gisanzwe cy'umuraba wa photon urangwa n'urumuri. Kubindi bisobanuro ku bipimo, reba ubushakashatsi bwabanje58. Nyuma yo kwiga uburyo bwo kubona electron yose (TEY)59 n'ikoreshwa ryayo muri X-PEEM, ubujyakuzimu bwo kubona ubu buryo bubarirwa kuri ~4–5 nm ku kimenyetso cya Cr na ~6 nm ku kimenyetso cya Fe. Ubujyakuzimu bwa Cr buri hafi cyane y'ubugari bwa oxide film (~4 nm)60,61 mu gihe ubujyakuzimu bwa Fe buruta ubugari bwa oxide film. XAS yakusanyijwe hafi y'inkombe ya Fe L ni uruvange rwa okiside y'icyuma XAS na FeO biva muri matrix. Mu rubanza rwa mbere, ubukana bwa elektroni zisohoka buterwa n'ubwoko bwose bushoboka bwa elektroni zigira uruhare muri TEY. Ariko, ikimenyetso cy'icyuma gisanzwe gisaba ingufu nyinshi za kinetike kugira ngo elektroni zinyure mu gice cya okiside, zigere hejuru, kandi zikusanyirizwe n'umuhanga mu gusesengura. Muri iki gihe, ikimenyetso cya Fe0 giterwa ahanini na elektroni za LVV Auger na elektroni za kabiri zisohoka nazo. Byongeye kandi, ubukana bwa TEY buterwa n'izi elektroni bubora mu gihe cyo gutoroka kwa elektroni49 burushaho kugabanya ikimenyetso cya spectral cya Fe0 mu ikarita ya XAS y'icyuma.
Gushyira amakuru mu tubumbe tw’amakuru (amakuru ya X-PEEM) ni intambwe y'ingenzi mu gukuramo amakuru ajyanye nayo (imiterere ya chimique cyangwa physique) mu buryo butandukanye. K-means clustering ikoreshwa cyane mu bice byinshi, harimo kureba imashini, gutunganya amashusho, kumenya imiterere idakurikiranywe, ubwenge bw’ubukorano, no gusesengura imiterere24. Urugero, K-means clustering ikoreshwa neza mu gukusanya amakuru y’amashusho ya hyperspectral62. Muri rusange, ku makuru y’ibintu byinshi, K-means algorithm ishobora kuyashyira mu byiciro byoroshye hakurikijwe amakuru yerekeye imiterere yayo (imiterere y’ingufu za photon). K-means clustering ni algorithm isubiramo yo kugabanya amakuru mu matsinda ya K adahurirana (amatsinda), aho buri pixel iba mu itsinda runaka bitewe n’uko imiterere ya chemical idahurirana mu byuma. K-means algorithm igizwe n’intambwe ebyiri: intambwe ya mbere ibara centroid za K, naho intambwe ya kabiri igaha buri ngingo itsinda rifite centroids zegeranye. Hagati y'uburemere bw'itsinda ritowe nk'ikigereranyo cy'amakuru y'ingingo z'amakuru (XAS spectra) z'iryo tsinda. Hari intera zitandukanye zo gusobanura centroids zegeranye nk'intera za Euclidean. Ku ishusho yinjiyemo px, y (x na y ni resolution muri pixels), CK ni yo hagati y'uburemere bw'itsinda; iyi shusho ishobora gucibwamo ibice (clustered) mu matsinda ya K hakoreshejwe K-means63. Intambwe za nyuma za algorithme ya K-means clustering ni:
Intambwe ya 2. Kubara urwego rw'ubunyamuryango bwa pikseli zose ukurikije centroid iriho ubu. Urugero, ibarwa uhereye ku ntera ya Euclidean d iri hagati y'aho hagati na buri pikseli:
Intambwe ya 3 Shyira buri pixel kuri centroid iri hafi. Hanyuma ongera ubare imyanya ya centroid ya K ku buryo bukurikira:
Intambwe ya 4. Subiramo inzira (ibigereranyo (7) na (8)) kugeza igihe centroids zihurira. Ibisubizo bya nyuma by'ubwiza bw'itsinda bifitanye isano rikomeye n'amahitamo meza ya centroids z'ibanze63. Ku miterere y'amakuru ya PEEM y'amashusho y'icyuma, ubusanzwe X (x × y × λ) ni agace k'amakuru ya 3D, mu gihe axes za x na y zigaragaza amakuru y'ahantu (resolution ya pixel) naho axis ya λ ihuye n'uburyo bwa spectral ya fotoni. Algorithm ya K-means yakoreshejwe mu gushakisha uturere dushishikajwe n'amakuru ya X-PEEM binyuze mu gutandukanya pixels (clusters cyangwa sub-blocks) hakurikijwe imiterere ya spectral yazo no gukuramo centroid nziza (XAS spectral curve) kuri buri analyte (cluster). Ikoreshwa mu kwiga ikwirakwizwa ry'ahantu, impinduka za spectral zo mu gace, imyitwarire ya oxidation n'imiterere ya shimi. Urugero, algorithm ya K-means clustering yakoreshejwe mu turere twa Fe L-edge na Cr L-edge mu bice bya X-PEEM ishyushye kandi ikonje. Imibare itandukanye ya K-clusters (uturere tw’imiterere mito) yageragejwe kugira ngo haboneke amatsinda na centroids byiza. Iyo mbonerahamwe igaragajwe, pixels zishyirwa kuri centroids z’amatsinda zikwiye. Buri tandukaniro ry’amabara rihuye n’aho hagati muri cluster riherereye, rikerekana imiterere y’ahantu hakorerwa ibintu bya shimi cyangwa physical. Centroids zakuwemo ni uruvange rw’umurongo wa spectra nziza.
Amakuru ashyigikira ibyavuye muri ubu bushakashatsi araboneka ku mwanditsi wa WC mu gihe abisabye mu buryo bwumvikana.
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